CN111224110A - Proton type solid oxide fuel cell cathode material and application thereof - Google Patents
Proton type solid oxide fuel cell cathode material and application thereof Download PDFInfo
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- CN111224110A CN111224110A CN201811423627.2A CN201811423627A CN111224110A CN 111224110 A CN111224110 A CN 111224110A CN 201811423627 A CN201811423627 A CN 201811423627A CN 111224110 A CN111224110 A CN 111224110A
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- cathode material
- solid oxide
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
- H01M4/8882—Heat treatment, e.g. drying, baking
- H01M4/8885—Sintering or firing
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
- H01M2004/8684—Negative electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention relates to a proton type solid oxide fuel cell cathode material which is characterized in that the cathode material has a general composition formula of BaCo0.6‑xFexM0.4‑yNyO3‑δM is one of Zr or Ce elements, N is one of Y or Yb elements, x is more than or equal to 0 and less than or equal to 0.6, Y is more than or equal to 0 and less than 0.4, and delta is more than 0 and less than or equal to 0.5. The cathode material has good matching property with the proton type solid oxide electrolyte at the common medium and low temperature, can meet the requirement of electrochemical performance by adjusting the cobalt-iron ratio, and solves the problem of lack of the cathode material of the proton type solid oxide fuel cell.
Description
Technical Field
The invention belongs to the field of solid oxide fuel cells, and particularly relates to a proton type solid oxide fuel cell cathode material.
Background
The proton type solid oxide fuel cell has the operating temperature of 350-650 ℃, and has the advantages of simple sealing, low cost, high stability and the like compared with the high-temperature operating environment of the traditional oxygen ion conduction type solid oxide fuel cell. At present, proton type solid oxide fuel cells are researched more in electrolyte aspect, and in cathode aspect, a medium-low temperature oxygen ion type cathode is generally applied to a proton type solid oxide fuel cell system, so that the problems of poor matching between an electrode and the electrolyte, fast performance attenuation, poor long-term stability and the like are caused. For example, the research shows that the BSCF has higher performance in proton type solid oxide, but has thermal matching and chemical compatibility with proton conductor electrolytePoor, easy to come off from the electrolyte surface and produce great interfacial resistance in the operation process, in addition easily take place first order phase transition under the atmosphere of low oxygen partial pressure, be difficult to satisfy long-term stable operation requirement. BaPrNi2O6-δSuch double-layer perovskite materials have been widely studied, but the matching and stability problems still remain. Therefore, a cathode material suitable for proton type solid oxide fuel cell systems is urgently needed in the field.
Disclosure of Invention
In order to solve the problems of matching and stability caused by taking a medium-low temperature oxygen ion type cathode as a proton type solid oxide fuel cell cathode, the invention provides a proton type solid oxide fuel cell cathode material which is characterized in that the cathode material has a general formula of BaCo0.6-xFexM0.4-yNyO3-δM is one of Zr or Ce, N is one of Y or Yb, x is more than or equal to 0 and less than or equal to 0.6, Y is more than or equal to 0 and less than 0.4, and delta is more than 0 and less than or equal to 0.5
The cathode material is characterized in that when M is Zr and N is Y, the cathode material is BaCo0.8-xFexZr0.2- yYyO3-δ。
The cathode material is characterized in that when x is 0.3 and y is 0.2, the cathode material is BaCo0.3Fe0.3Zr0.2Y0.2O3-δ。
The cathode material is characterized in that when M is Ce and N is Yb, the cathode material is BaCo0.8-xFexCe0.2- yYbyO3-δ。
The cathode material is characterized in that when x is 0.2 and y is 0.1, the cathode material is BaCo0.4Fe0.2Ce0.3Yb0.1O3-δ。
The cathode material is characterized in that the cathode material can be applied to BaCeO3Radical, BaZrO3Group, SmNiO3And proton type solid oxide electrolyte.
The invention has the beneficial effects that: solves the problems of the traditional method in low or mediumThe performance of the cathode of the proton type solid oxide fuel cell is greatly reduced by changing BaCo0.6-xFexM0.4-yNyO3-δThe medium-low temperature cathode has high catalytic performance, good stability and good matching property with various proton type electrolytes, solves the problem that the conventional cathode material is deficient in the research of proton type solid oxide fuel cells, and provides a new idea for the research and preparation of proton type solid oxides.
Detailed Description
Example 1
Mixing Ba (NO)3)2，Co(NO3)2·6H2O，Fe(NO3)3·9H2O，Zr(NO3)4·5H2O，Y(NO3)3·6H2O, adding the mixture into 250mL of deionized water according to the mol ratio of 1:0.3:0.3:0.2:0.2, and heating and stirring the mixture at 80 ℃ until the solution is clear. Then 0.25mol of glycine is weighed and added according to the molar ratio of nitrate radical to glycine of 1:1.0, the pH value is adjusted to 7 by ammonia water, and the solution is heated and evaporated until the solution is gelatinous under continuous stirring. BaCo obtained by self-propagating combustion method0.3Fe0.3Zr0.2Y0.2O3-δAnd (3) primary powder is roasted for 2 hours at the temperature of 1000 ℃ to obtain final powder. Adding terpineol (the mass ratio of terpineol to powder is 0.4:1) containing 6 wt% of ethyl cellulose into the cathode powder, and uniformly grinding to obtain cathode slurry. The resulting slurry was coated to a thickness of 10 microns with BaZr0.8Y0.2O3-δBaZr of0.8Y0.2O3-δAnd (6) sintering the surface of the anode support membrane of + NiO for 2h at 900 ℃ to obtain the BCFZY/BZY/BZY-NiO battery. And (3) carrying out performance test on the battery under the working conditions that: at 15mL/minH2Is fuel gas; 20mL/min of air is taken as an oxidant, 0.8V is discharged for 5h at 600 ℃, the open-circuit voltage is 1.192V, and the power density can reach 338mW cm at 500 DEG C2。
Example 2
Mixing Ba (NO)3)2，Co(NO3)2·6H2O，Fe(NO3)3·9H2O，Ce(NO3)3·6H2O，Yb(NO3)3·6H2O, adding the mixture into 200mL of deionized water according to the mol ratio of 1:0.3:0.3:0.2:0.2, and heating and stirring the mixture at 80 ℃ until the solution is clear. Then 0.24mol of glycine is weighed and added according to the molar ratio of nitrate radical to glycine of 1:1.0, the pH value is adjusted to 6 by ammonia water, and the solution is heated and evaporated until the solution is gelatinous under continuous stirring. BaCo obtained by self-propagating combustion method0.3Fe0.3Ce0.2Yb0.2O3-δAnd (3) primary powder is roasted for 2 hours at the temperature of 1000 ℃ to obtain final powder. Adding terpineol (the mass ratio of terpineol to powder is 0.4:1) containing 6 wt% of ethyl cellulose into the cathode powder, and uniformly grinding to obtain cathode slurry. The resulting slurry was coated to plate 15 micron thick BaCe0.8Yb0.2O3-δBaCe of (1)0.8Yb0.2O3-δAnd sintering the surface of the anode support film at 900 ℃ for 2h to obtain the BCFZYb/BCYb/BCYb-NiO battery. And (3) carrying out performance test on the battery under the working conditions that: at a rate of 10mL/minH2Is fuel gas; 20mL/min of air is taken as an oxidant, 0.8V is discharged for 2h at 600 ℃, the open-circuit voltage is 1.202V, and the power density can reach 103mW cm at 450 DEG C2。
Example 3
Mixing Ba (NO)3)2，Co(NO3)2·6H2O，Fe(NO3)3·9H2O，Ce(NO3)3·6H2O，Yb(NO3)3·6H2O, adding the mixture into 250mL of deionized water according to the mol ratio of 1:0.4:0.2:0.3:0.1, and heating and stirring the mixture at 80 ℃ until the solution is clear. Then 0.25mol of glycine is weighed according to the molar ratio of nitrate radical to glycine of 1:1.0, ammonia water is used for adjusting the pH value to 8, and the solution is heated continuously to evaporate water until the solution is gelatinous. BaCo obtained by self-propagating combustion method0.4Fe0.2Ce0.3Yb0.1O3-δAnd (3) primary powder is roasted for 2 hours at the temperature of 1000 ℃ to obtain final powder. Adding terpineol (the mass ratio of terpineol to powder is 0.4:1) containing 6 wt% of ethyl cellulose into the cathode powder, and uniformly grinding to obtain cathode slurry. The resulting slurry was coated to plate 10 micron thick BaCe0.7Zr0.1Yb0.2O3-δBCe (g)0.7Zr0.1Yb0.2O3-δAnd (6) sintering the NiO anode supporting film surface at 900 ℃ for 2h to obtain the BCFZYb/BCZYb/BCZYb-NiO battery. And (3) carrying out performance test on the battery under the working conditions that: at a rate of 20mL/minH2Is fuel gas; 20mL/min of air is taken as an oxidant, 0.8V is discharged for 3h at 600 ℃, the open-circuit voltage is 1.172V, and the power density can reach 419mW cm at 550 DEG C2。
Claims (7)
1. The proton type solid oxide fuel cell cathode material is characterized in that the cathode material has a general composition formula of BaCo0.6-xFexM0.4-yNyO3-δM is one or two of Zr or Ce elements, N is one or two of Y or Yb elements, x is more than or equal to 0 and less than or equal to 0.6, Y is more than or equal to 0 and less than 0.4, and delta is more than 0 and less than or equal to 0.5.
2. The cathode material according to claim 1, wherein when M is Zr and N is Y, the cathode material is BaCo0.8-xFexZr0.2-yYyO3-δ。
3. The cathode material according to claim 2, wherein when x is 0.3 and y is 0.2, the cathode material is BaCo0.3Fe0.3Zr0.2Y0.2O3-δ。
4. The cathode material of claim 1, wherein when M is Ce and N is Yb, the cathode material is BaCo0.8-xFexCe0.2-yYbyO3-δ。
5. The cathode material according to claim 4, wherein when x is 0.2 and y is 0.1, the cathode material is BaCo0.4Fe0.2Ce0.3Yb0.1O3-δ。
6. A kind ofThe use of the cathode material as claimed in any one of claims 1 to 5, wherein the cathode material is applicable to BaCeO3Radical, BaZrO3Radical or SmNiO3And proton type solid oxide electrolyte.
7. Use of the cathode material according to any one of claims 1 to 5 as a cathode material in a proton type solid oxide fuel cell cathode.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114447384A (en) * | 2022-01-26 | 2022-05-06 | 湖北大学 | A-site defective perovskite structure fuel cell electrolyte, preparation method thereof and fuel cell |
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| US20120204716A1 (en) * | 2009-08-31 | 2012-08-16 | Borsig Process Heat Exchanger Gmbh | Ceramic membrane having a catalytic membrane-material coating |
| US20160301070A1 (en) * | 2015-01-08 | 2016-10-13 | Colorado School Of Mines | Cathode material for low temperature solid oxide fuel cells |
| CN108091913A (en) * | 2016-11-23 | 2018-05-29 | 清华大学 | The preparation method of Solid-state fuel cell and solid electrolyte |
| CN108448125A (en) * | 2018-04-12 | 2018-08-24 | 中国矿业大学 | A kind of cathode material and preparation method of proton conductor solid oxide fuel cell |
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- 2018-11-27 CN CN201811423627.2A patent/CN111224110A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120204716A1 (en) * | 2009-08-31 | 2012-08-16 | Borsig Process Heat Exchanger Gmbh | Ceramic membrane having a catalytic membrane-material coating |
| US20160301070A1 (en) * | 2015-01-08 | 2016-10-13 | Colorado School Of Mines | Cathode material for low temperature solid oxide fuel cells |
| CN108091913A (en) * | 2016-11-23 | 2018-05-29 | 清华大学 | The preparation method of Solid-state fuel cell and solid electrolyte |
| CN108448125A (en) * | 2018-04-12 | 2018-08-24 | 中国矿业大学 | A kind of cathode material and preparation method of proton conductor solid oxide fuel cell |
Non-Patent Citations (1)
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| CN114447384A (en) * | 2022-01-26 | 2022-05-06 | 湖北大学 | A-site defective perovskite structure fuel cell electrolyte, preparation method thereof and fuel cell |
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